Single crystals of K(Th0.75Sr0.25)2Se6 were obtained by a standard solid-state chemistry route at 1173 K. This compound does not belong to the AAn2Q6 family (A = K, Rb, Cs, or Tl; An = Th, U, or Np; Q = S, Se, or Te) that possesses infinite Q-Q-Q chains and where a charge distribution of A+, 2 × An4+, 2 × Q2-, 2 × (Q22.5-) has been proposed and hence a charge of -1.25 on Q of the "dichalcogenide". Rather in K(Th0.75Sr0.25)2Se6, where the Th and Sr cations randomly occupy the same site, incorporation of these differently charged cations breaks the infinite Se-Se-Se chains into a structure that has typical Se22- pairs. © 2018 American Chemical Society.